EP2971562B1 - Composite à matrice céramique et revêtements de barrière environnementale résistant à l'usure - Google Patents

Composite à matrice céramique et revêtements de barrière environnementale résistant à l'usure Download PDF

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EP2971562B1
EP2971562B1 EP14712929.0A EP14712929A EP2971562B1 EP 2971562 B1 EP2971562 B1 EP 2971562B1 EP 14712929 A EP14712929 A EP 14712929A EP 2971562 B1 EP2971562 B1 EP 2971562B1
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silicon
oxide
layer
substrate
article
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EP2971562A1 (fr
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Krishan Lal Lal LUTHRA
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General Electric Co
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General Electric Co
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
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    • C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/284—Selection of ceramic materials
    • C—CHEMISTRY; METALLURGY
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00405—Materials with a gradually increasing or decreasing concentration of ingredients or property from one layer to another
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/50—Intrinsic material properties or characteristics
    • F05D2300/514—Porosity
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
    • F05D2300/603—Composites; e.g. fibre-reinforced
    • F05D2300/6033—Ceramic matrix composites [CMC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

  • the disclosure relates generally to ceramic matrix composites. More particularly, embodiments herein generally describe recession resistant ceramic matrix composites, coatings and related articles and methods used in the gas turbine and aerospace industries.
  • Ceramic matrix composites are a class of materials that consist of a reinforcing material surrounded by a ceramic matrix phase, and are currently proposed for use for higher temperature applications. Ceramic matrix composites can decrease the weight, yet maintain the strength and durability, of turbine articles used in higher temperature sections of gas turbine engines, such as airfoils (blades and vanes), combustors, shrouds and other like articles that would benefit from the lighter-weight these materials can offer.
  • EBCs environmental barrier coatings
  • US 7 740 7960 B1 discloses a multilayer coating system providing a protective coating solution for silicon-based ceramic components exposed to very high temperatures and/or high gas flow velocity water vapor combustion environments.
  • EP 2 284 139 A2 discloses an environmental barrier coating for high temperature ceramic components comprising a bond coat layer, an optional silica layer and at least one transition layer.
  • EBCs typically develop local spalls, caused by foreign object damage or handling damage. For most hot stage articles, it is believed that this results in high volatilization rates locally in the region of spalls resulting in the formation of holes in the CMC articles, and in turn causing recession of the CMC over time. This recession of the CMCs is considered one of the main obstacles in commercialization of CMCs. Modeling and experiments indicate that EBC spallation in some regions of engine articles can lead to burn through of the CMC. The ceramic community has been working for years to solve this problem. As such, the gas turbine and aerospace industries are continuously looking for new and improved CMCs and related articles and processes.
  • X H 2 O is the mole fraction of water vapor.
  • the above equation was derived using testing on flat samples under laminar flow conditions.
  • the gas turbine articles are much more complex in shape, and consequently equations based on flat plate geometry are not appropriate.
  • the flow conditions during gas turbine operation are turbulent. Nevertheless, no one has developed equations for recession in turbine conditions, and the above equation is used for turbine operation.
  • X H 2 O is the mole fraction of water vapor
  • h is the heat transfer coefficient in BTU.h -1 ft -2o P -1
  • P is the pressure in atm
  • T is the temperature in ° K .
  • the above equation was developed using Reynold's analogy between the heat and mass transfer.
  • the water vapor level depends on the type of fuel and air to fuel ratio and can range from 4% to as high as 19%.
  • EBCs are used to protect silicon-containing ceramics against recession.
  • silicon carbide forms carbon oxides which destroy the integrity of the EBCs. Therefore, Applicants developed coatings that use silicon as a bond coat ( U.S. Patent No. 6,299,988 ).
  • silicon melts at about 1410°C (2570 F) and softens at even lower temperatures. Therefore, the inventor of the instant application saw the need for another coating system for temperatures over about 1371°C (2500 F).
  • Figure 3 shows a schematic representation of various rate limiting steps during the gas phase mass transport.
  • Interface reactions are generally fairly rapid, and it is reasonable to assume that the rate is limited by gas phase transport. However, it is possible that under takeoff conditions, where the heat transfer and mass transfer coefficients are extremely high, the interface reaction might play a role and reduce the recession rate.
  • Hot stage articles of gas turbines are exposed to turbulent gas flow conditions where the volatilization primarily occurs by convective flow.
  • the volatilization or recession rate under the turbine conditions is believed to be controlled by gas phase mass transport.
  • the partial pressure of water vapor is orders of magnitude higher than that of silicon hydroxides. Consequently, the volatilization (recession) cannot be controlled by water vapor transport.
  • the instant disclosure teaches that a porous layer that is significantly larger than the effective boundary layer thickness ( see Figure 5 ) would act as a diffusion barrier layer and reduce the recession rate of the underlying substrate.
  • the effectiveness of the porous layer is more than would be expected from just the thickness effect because the porosity in the porous layer also reduces the cross-sectional area through which diffusion can occur as well as the tortuosity of the diffusion path.
  • the effective diffusion distance for a porous layer can be expressed as
  • Heat transfer calculations indicate that in the presence of a TBC spall the local heat transfer conditions are similar to those on the surface of the article. If the heat transfer conditions in the spalled region are similar to those on the surface, the recession rate of the substrate would be unacceptably high, and could lead to formation of holes in the CMC articles in spalled regions. Recession of the CMC and resulting formation of holes in the CMC article is considered to be a major obstacle in commercialization of CMCs.
  • the Rare Earth Silicate oxide layer can be at least one rare-earth oxide-containing compound containing an oxide of an element chosen from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and/or Lu.
  • the oxide layer comprises hafnium oxide and/or barium strontium aluminosilicate
  • the oxide layer itself can be graded with an inner layer and an outer layer, such that the inner layer is chemically stable with silicon oxide and the outer layer has a higher stability in water vapor environment than the inner layer.
  • the inventor of the instant application has surprisingly discovered that it is advantageous to deposit a layer of a chemically stable porous oxide layer on a silicon-containing substrate.
  • the porous oxide layer consists of oxide materials that may be deposited with special microstructures to mitigate thermal or mechanical stresses due to thermal expansion mismatch or contact with other articles in the engine environment and to improve adhesion of the coating to the substrate.
  • Embodiments of the disclosure described herein relate to ceramic matrix composites (CMC) and coatings.
  • CMC ceramic matrix composites
  • the inventor of the instant application has discovered, in one example, that improved recession resistant CMC can be achieved by replacing the silicon bond coat with a three layer bond coat system comprising a first layer of silicon, followed by a layer of silicon and an oxide, followed by a layer of silicon ( see Figure 13B ).
  • Conventional oxide EBCs can be put on top of this bond coat system,
  • the recession resistant article may comprise a silicon-containing substrate (or a silicon alloy) having a first coefficient of thermal expansion; and a bond coat comprising a two phase layer of interconnected silicon and interconnected oxide, followed by a layer of silicon, wherein the bond coat is located on top of the substrate to form the recession resistant silicon containing article.
  • the article may further comprise one or more additional oxide layers of the Environmental Barrier Coating on the surface.
  • the local spallation of the EBC still occurs substantially at the interface between the silicon bond coat and the outside oxide EBC.
  • the oxide in the silicon-oxide layer is stable under the water vapor environments of the gas turbine. Reaction of the water vapor with the oxide is such that the changes still keep the integrity of the porous oxide layer.
  • Figure 13 shows a schematic, depicting that the disclosure also teaches a recession resistant article for a gas turbine engine, where the article comprises a silicon-containing substrate which has a silicon bondcoat bonded to at least a portion of its outer surface.
  • the article further comprises interconnected silicon and an oxide layer positioned between the substrate material and the silicon bondcoat.
  • the interconnected silicon and oxide layer has as second coefficient of thermal expansion, and there is about 20% or less difference between the value of the first and second coefficients of thermal expansion.
  • the article may further comprise a silicon layer located between the substrate and the two phase layer.
  • the substrate may be a silicon alloy.
  • the silicon containing ceramic may be a silicon nitride, silicon carbide, silicon oxinitride, a metal silicide, a ceramic matrix composite material, and combinations thereof.
  • Some oxides of interest include Rare Earth Disilicate and Alkaline Earth Monosilicates.
  • the silicon containing ceramic of the present disclosure can be selected from the group consisting of silicon nitride, silicon carbide, silicon oxinitride, a metal silicide, a ceramic matrix composite material, and combinations thereof
  • the oxide can have an expansion coefficient of about 5 ppm per degree C; and the oxide can be chemically stable in moisture containing environments and/or exhibit no more than about 30% negative volume change associated with reaction with water vapor; and such that the oxide is chemically stable with silicon oxide.
  • the oxide may be a Rare Earth Disilicate with an oxide of the element Y and/or Yb and/or Lu.
  • the oxide may be an Alkaline Earth Aluminosilicate with Alkaline Earth Silicate comprising alkaline earth of one or more of the elements of Ba Sr. Ca, and Mg.
  • one aspect of the present disclosure is directed to a method for fabricating a recession resistant article for a gas turbine engine.
  • the method comprises providing a silicon containing substrate having a first coefficient of thermal expansion; and bonding a two layer bond coat to at least a portion of an outer surface of the article, wherein the two layer bond coat comprises a layer of interconnected silicon and an oxide, followed by a layer of silicon, and wherein said two layer bond coat has a second coefficient of thermal expansion (see Figures 13 and 14 ).
  • the method may further comprise placing a layer of silicon between the substrate and the two phase silicon and oxide layer.
  • Figure 15B shows that the recession problem can be alleviated by adding oxide particles to the CMC substrate.
  • oxide particles When the CMC substrate is exposed to the water vapor environments, silicon carbide constituents volatilize leaving oxides behind. The porous oxide film left behind provides protection against recession, thereby reducing the recession rate of the substrate.
  • oxides can be added to the current MI CMCs or to the other composites, such as CVI composites during the fabrication of the preform.
  • the oxides have low thermal conductivity, which is not desirable for some applications. Therefore, the oxide addition may be tailored to be included at a location where recession resistance of the CMC is important.
  • the inventor of the instant application conceived that particular oxides would work, for example those that meet some specific criteria, including: an expansion coefficient of around 5 ppm per degree C, and in one example within 4-6 ppm per degree C, (ii) chemically stable in moisture-containing environments, and/or minimal negative volume change associated with reaction with water vapor, and (iii) in one example, also chemically stable with silicon oxide.
  • the oxide may be a Rare Earth Disilicate with an oxide of the element Y and/or Yb and/or Lu.
  • Such conventional methods can generally include, but should not be limited to, plasma spraying, high velocity plasma spraying, low pressure plasma spraying, solution plasma spraying, suspension plasma spraying, high velocity oxygen flame (HVOF), chemical vapor deposition (CVD), electron beam physical vapor deposition (EBPVD), sol-gel, sputtering, slurry processes such as dipping, spraying, tape-casting, rolling, and painting, and combinations of these methods.
  • the substrate article may be dried and sintered using either conventional methods, or unconventional methods such as microwave sintering, laser sintering or infrared sintering.
  • the surface layer containing the oxide powder is then melt infiltrated along with the rest of the CMC preform to form an integral surface layer containing the desired oxide particles.
  • the slurry containing the oxide particles can be coated onto a CMC preform by techniques such as spray painting or dip coating, followed by melt infiltration.
  • oxide particles are added to the matrix precursor slurry and then to prepreg composite tapes with this slurry. CMC components are then laid up using such tapes. Oxides particles have much lower thermal conductivity than the silicon carbide, and this may not be desirable for some applications or some locations of the components.
  • the presently taught method can, in one example, be tailored so that the oxide addition is not uniformly in the composite but is selectively done in the desired locations of the component.
  • the method may further comprise melt infiltrating the surface layer containing the oxide along with the rest of the ceramic matrix composite preform with molten silicon or silicon-containing alloy to form a surface layer containing the oxide particles.
  • the oxide containing slurry may be coated onto a ceramic matrix composite preform.
  • the coating may be performed by spray painting or dip coating, followed by melt infiltration.
  • Another aspect of the present disclosure is directed to a method of making the surface coating on the Si-containing substrate, wherein the coating is made by making a mixture of a silicon ceramic precursor polymer and the oxide particles, coating the said mixture on the surface of the silicon-containing substrate, heat treating the coated surface to convert the polymer into the ceramic.
  • the polymer impregnation and subsequent heat treatment may be repeated after depositing the first coating.
  • Another example of creating the surface layer is that it can be applied to CMCs made by other techniques including CVI and PIP.
  • Examples of CMC matrix materials include silicon carbide and silicon nitride.
  • Examples of CMC reinforcing materials include, but are not limited to, silicon carbide, and silicon nitride.
  • Examples of silicon carbide fibers include all commercially available fibers known as silicon carbide fibers, which comprise silicon carbide and may also contain other elements, such as oxygen, carbon, nitrogen, aluminum, and others. Examples of known silicon carbide fibers are the NICALONTM family of silicon carbide fibers available from Nippon Carbon, Japan; SylramicTM silicon carbide fibers available from COI/ATK, Utah the TyrarnnoTM family of fibers available from UBE Industries, Japan; and fibers having the trade name SCS-6 or SCS-Ultra produced by Specialty Materials, Inc., Massachusetts. Examples of monolithic ceramics include silicon carbide, silicon nitride, and silicon aluminum oxynitride (SiAlON).
  • the silicon-containing substrate may be deposited by a CVD process, and the oxide may be deposited by a plasma spraying process or a slurry coating process.
  • silicon in the two phase silicon-oxide layer may be replaced with silicon carbide or silicon nitride.
  • the article or component may comprise a part of a gas turbine assembly.
  • the article or component can be selected from the group consisting of combustor articles, turbine blades, shrouds, nozzles, heat shields and vanes.
  • the CMC material may be a SiC/SiC CMC material.
  • the SiC-SiC CMC material includes a silicon carbide composite material infiltrated with silicon and reinforced with coated silicon carbide fibers.
  • the ceramic material may be a monolithic ceramic material, such as SiC.
  • the silicon containing substrate may be a ceramic and selected from the group consisting of silicon nitride, silicon carbide, silicon oxinitride, a metal silicide, a ceramic matrix composite material, and combinations thereof.
  • the ceramic matrix composite in one example, comprises a SiC ⁇ SiC ceramic matrix composite,
  • Rare Earth Elements include scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and mixtures thereof
  • Rare Earth Silicate Oxides can refer to silicates of Sc 2 O 3 , Y 2 O 3 , CeO 2 , La 2 O 3 , Pr 2 O 3 , Nd 2 O 3 , Pm 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , HO 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 or mixtures thereof.
  • the group consisting of oxides may include Alkaline Earth Aluminosilicates.
  • the oxide may be a Rare Earth Disilicate with an oxide of an element chosen from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or combination thereof.
  • the oxide may be a Rare Earth Disilicate with an oxide of the element Y and/or Yb and/or Lu.
  • the oxide is hafnium oxide.
  • the oxide may also be an Alkaline Earth Aluminosilicate comprising alkaline earth of one or more of the elements of Ba Sr, Ca, and Mg.
  • Alkaline Earth Elements within the scope of the present disclosure include magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and mixtures thereof. Additionally, rare earth elements include scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (T
  • REDs such as yttrium/ytterbium disilicate
  • Alkaline Earth Aluminosilicates such as Barium Strontium aluminosilicate.
  • the silicon containing ceramic is selected from the group consisting of silicon nitride, silicon carbide, silicon oxinitride, a metal silicide, a ceramic matrix composite material, and combinations thereof.
  • the oxide has an expansion coefficient of about 5 ppm per degree C; wherein the oxide is chemically stable in moisture containing environments and/or exhibits no more than about 30% negative volume change associated with reaction with water vapor; and wherein the oxide is chemically stable with silicon oxide.
  • the oxide is a Rare Earth Disilicate with an oxide of the element Y and/or Yb and/or Lu.
  • the oxide is an Alkaline Earth Aluminosilicate comprising Alkaline Earth Silicate of one or more of the elements of Ba Sr, Ca, and Mg.
  • the recession resistant silicon containing article of the present disclosure further comprises a protective porous oxide layer formed in-situ after the outer oxide layer of the EBC spalls during operation of the gas turbine engine component.
  • the recession resistant silicon containing article of the present disclosure further comprises volatization of silicon from the silicon containing article, such that the rate of recession of the underlying substrate drops by a factor of between 5 and 100 when compared to control recession rates after at least a portion of the outer oxide layers of the EBC spall off.
  • the layer of interconnected silicon and an oxide has a second coefficient of thermal expansion, and wherein the difference in value between the first and second coefficient of thermal expansion is no more than about 20%.
  • the article further comprises a silicon layer located between the substrate and the two phase layer.
  • One aspect of the present disclosure is directed to a recession resistant article for a gas turbine engine, said article comprising: a substrate material comprising silicon, wherein said substrate material has a first coefficient of thermal expansion; a silicon bondcoat bonded to at least a portion of an outer surface of said substrate material; an interconnected silicon and an oxide layer positioned between the substrate material and the silicon bondcoat, wherein said interconnected silicon and oxide layer has a second coefficient of thermal expansion, wherein there is about 20% or less difference between the value of the first and second coefficients of thermal expansion.
  • the substrate is a ceramic matrix composite
  • the bond coat comprises a layer of 5% to 50% (by volume) of interconnected silicon and 50% to 95% oxide, followed by a layer of silicon.
  • the article further comprises a layer of silicon between the substrate the interconnected silicon-oxide layer.
  • the first layer of silicon is up to about 10 mils thick
  • the second layer of interconnected silicon and oxide layer is from about 0,0508 mm (2 mils) to about 0,508 mm (20 mils) thick
  • the third layer is from about 2 mils to about 10 mils thick.
  • the recession resistant article in one example, further comprises an environmental barrier coating on top of the three layer bond coat.
  • the structure of the interconnected silicon and interconnected oxide is in the form of vertical arrays, lattice arrays, or parallel arrays; wherein in the vertical arrays, the interconnected silicon and interconnected oxide are vertical arrays roughly normal to the surface of the substrate; wherein in the lattice arrays, the interconnected silicon and interconnected oxide are in the form of a lattice or grid relative to the surface of the substrate; and wherein in the parallel arrays, the interconnected silicon and interconnected oxide are parallel to each other relative to the surface of the substrate.
  • the silicon-containing substrate is, in one example, deposited by a CVD process. In one embodiment, the oxide is deposited by a plasma spraying process or a slurry coating process.
  • One aspect of the present disclosure is directed to a method for fabricating a recession resistant article for a gas turbine engine, said method comprising: providing a silicon containing substrate having a first coefficient of thermal expansion; and bonding a two layer bond coat to at least a portion of an outer surface of the article, wherein the two layer bond coat comprises a layer of interconnected silicon and an oxide, followed by a layer of silicon, and wherein said two layer bond coat has a second coefficient of thermal expansion.
  • the method further comprises placing a layer of silicon between the substrate and the two phase silicon and oxide layer.
  • the method further comprises bonding a surface layer comprising an environmental barrier coating on top of the three layer bond coat.
  • the method further comprises volatization of silicon from the substrate and the in-situ formation of a protective porous oxide layer over the substrate after the outer oxide layer of the EBC spalls during operation of the gas turbine engine article.
  • the method of the present disclosure further comprises volatization of silicon from the silicon containing article, such that the rate of recession of the underlying substrate drops by a factor of between 5 and 100 when compared to control recession rates after at least a portion of the outer oxide layers of the EBC spall off. In some conditions, particularly with thick porous layers, the benefits may even be higher than by a factor of 100. In one embodiment, there is about 20% or less difference between the value of the first and second coefficients of thermal expansion.
  • a recession resistant article comprising an oxide in a silicon containing substrate, wherein components of the silicon containing substrate is interconnected with oxides dispersed in the substrate and form the bulk of the recession resistant silicon containing article.
  • both the silicon-containing substrate and the oxide phases are interconnected independent networks.
  • the substrate comprises a SiC--SiC ceramic matrix composite.
  • the oxide has an expansion coefficient of about 5 ppm per degree C; wherein the oxide is chemically stable in moisture containing environments and/or exhibits minimal negative volume change associated with reaction with water vapor (for e.g., no more than 30%).
  • the oxide is chemically stable with silicon oxide.
  • the article is a gas turbine engine component and wherein said component contains, by volume, about 10% to 60% of the rare-earth silicate oxide containing compound, preferably between about 20 and 40%,
  • the oxide is a Rare Earth Disilicate with an oxide of one or more elements selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • the oxide is, in one example, a Rare Earth Disilicate with an oxide of the element Y and/or Yb and/or Lu.
  • the oxide is hafnium oxide.
  • the oxide is an Alkaline Earth Aluminosilicate comprising Alkaline Earth Silicate of one or more of the elements of Ba Sr, Ca, and Mg.
  • the article further comprises a bond coat located on top of the substrate.
  • the substrate is a ceramic matrix composite
  • the bond coat comprises a layer of interconnected silicon and an oxide, followed by another layer of silicon.
  • the article further comprises a silicon layer between the substrate and the two phase silicon and oxide layer.
  • the recession resistant article of the present disclosure in one example, further comprises an environmental barrier coating on top of the bond coat.
  • the substrate is coated with an environment barrier coating that is from about 0,0508 mm (2 mils) to about 1,27 mm (50 mils) thick.
  • the substrate is made by a process of polymer impregnation pyrolysis, chemical vapor infiltration, melt infiltration, sintering, and combination thereof.
  • the substrate is made by a process of silicon melt infiltration.
  • the article comprises a component of a gas turbine assembly.
  • the recession resistant article is a gas turbine engine component selected from the group consisting of combustor components, turbine blades, shrouds, nozzles, heat shields and vanes.
  • One aspect of the present disclosure is directed to a recession resistant gas turbine component, comprising a silicon containing substrate that has an oxide within it, wherein components of the silicon containing substrate and the oxide are interconnected and/or interwoven with one another.
  • the oxide has an expansion coefficient of about 5 ppm per degree C; wherein the oxide is chemically stable in moisture containing environments and/or exhibits no more than about 30% negative volume change associated with reaction with water vapor; and wherein the oxide is chemically stable with silicon oxide.
  • Another aspect of the present disclosure is directed to a method of making a preform for melt infiltration, comprising: a) providing a ceramic matrix precursor slurry; b) incorporating one or more Rare Earth Disilicates (RE 2 Si 2 O 7 ) and/or one or more of Alkaline Earth Aluminosilicates (RE 2 SiO 5 ) into said matrix precursor slurry; c) impregnating the slurry into a carbon veil material or tape casting the slurry to yield a thin sheet of matrix precursor; d) positioning said sheet on the surface of the ceramic matrix composite preform to form a surface layer containing the oxide particles; and e) consolidating said sheet onto the preform using vacuum bagging and lamination or compression molding.
  • a ceramic matrix precursor slurry comprising: a) providing a ceramic matrix precursor slurry; b) incorporating one or more Rare Earth Disilicates (RE 2 Si 2 O 7 ) and/or one or more of Alkaline Earth Aluminosilicates (RE 2 SiO
  • the method farther comprises melt infiltrating the surface layer containing the oxide along with the rest of the ceramic matrix composite preform with molten silicon or silicon-containing alloy to form a surface layer containing the oxide particles.
  • the oxide containing slurry is coated onto a ceramic matrix composite preform.
  • the said coating is performed by spray painting or dip coating, followed by melt infiltration.
  • One aspect of the present disclosure is directed to a method of making a preform for melt infiltration, comprising: a) providing a ceramic matrix precursor slurry; b) incorporating one or more oxides, wherein the oxide is one or more rare-earth disilicates (RE 2 Si 2 O 7 ) and/or one or more of Alkaline Earth Aluminosilicates (RE 2 SiO 5 ) into said matrix precursor slurry; wherein the oxide particles are added to the matrix precursor slurry and the composite tape is subsequently prepreged with the slurry, the prepregged tapes are laid up and consolidated into a composite preform, and the preform is subsequently melt infiltrated with silicon or silicon alloy.
  • the oxide is one or more rare-earth disilicates (RE 2 Si 2 O 7 ) and/or one or more of Alkaline Earth Aluminosilicates (RE 2 SiO 5 ) into said matrix precursor slurry; wherein the oxide particles are added to the matrix precursor slurry and the composite tape is
  • Another aspect of the present disclosure is directed to a method of making the surface coating on the Si-containing substrate, wherein the coating is made by making a mixture of a silicon ceramic precursor polymer and the oxide particles, coating the said mixture on the surface of the silicon-containing substrate, heat treating the coated surface to convert the polymer into the ceramic.
  • the polymer impregnation and subsequent heat treatment are repeated after depositing the first coating.

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Claims (16)

  1. Article de moteur à turbine à gaz résistant au retrait, comprenant un substrat contenant du silicium revêtu d'une couche d'oxyde poreuse chimiquement stable, ladite couche d'oxyde poreuse étant d'environ 1 millième de pouce à environ 50 millièmes de pouce d'épaisseur et ladite couche d'oxyde poreuse protégeant le substrat du retrait dans des environnements gazeux chauds, le substrat comprenant un composite à matrice céramique SiC-SiC ;
    la couche d'oxyde poreuse comprenant un mélange diphasique d'un oxyde et d'un composé contenant du silicium ;
    l'oxyde comprenant un ou plusieurs disilicates de terres rares (RE2Si2O7), aluminosilicates alcalino-terreux et monosilicates de terres rares (RE2SiO5) ;
    une couche intermédiaire étant utilisée entre le substrat et la couche d'oxyde afin d'améliorer l'intégrité structurelle du substrat au moyen de la couche poreuse, ladite couche intermédiaire comprenant un oxyde et un silicium ou un composé contenant du silicium, un mélange diphasique de silicium ou carbure de silicium et d'un disilicate de terres rares, ou un mélange diphasique de nitrure de silicium et d'un monosilicate de terres rares.
  2. Article de turbine à gaz selon la revendication 1, ladite couche poreuse contenant une porosité d'environ 5 à 50 %.
  3. Article de turbine à gaz selon la revendication 1, la couche d'oxyde comprenant au moins un composé contenant de l'oxyde de terres rares contenant un oxyde d'un élément choisi dans le groupe constitué de Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, ou une combinaison de ceux-ci.
  4. Article de turbine à gaz selon la revendication 1, le composé contenant du silicium de la couche d'oxyde poreuse comprenant un composé contenant du silicium choisi dans le groupe constitué de silicium, carbure de silicium, nitrure de silicium, ou siliciure de molybdène.
  5. Article de turbine à gaz selon la revendication 1, la porosité de ladite couche étant calibrée pour fournir une intégrité structurelle mécanique à l'interface du substrat/revêtement.
  6. Article de turbine à gaz selon la revendication 1, la couche d'oxyde étant chimiquement stable au moyen de l'oxyde de silicium et ayant un coefficient de dilatation d'environ 5 ppm par degré C.
  7. Article de moteur à turbine à gaz selon la revendication 8, la couche d'oxyde poreuse étant créée in situ lors de l'utilisation par volatilisation d'un composé contenant du silicium.
  8. Article de moteur à turbine à gaz selon la revendication 5, la couche poreuse calibrée comportant une couche intérieure et une couche extérieure, la couche intérieure étant chimiquement stable au moyen de l'oxyde de silicium et la couche extérieure ayant une plus grande stabilité dans un environnement de vapeur d'eau que la couche intérieure.
  9. Article de moteur à turbine à gaz selon la revendication 5, la couche intérieure étant un disilicate de terres rares (RE2Si2O7) et la couche extérieure étant un monosilicate de terres rares (RE2SiO5), RE étant un élément choisi dans le groupe constitué de Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, ou une combinaison de ceux-ci.
  10. Article de moteur à turbine à gaz selon les revendications 1 à 9, la couche poreuse comprenant de l'oxyde d'hafnium et/ou d'aluminosilicate de baryum et de strontium.
  11. Article de moteur à turbine à gaz selon les revendications 1à 9, la structure de l'oxyde et d'un composé contenant du silicium étant sous forme de réseaux verticaux, réseaux en treillis ou réseaux parallèles.
  12. Article de moteur à turbine à gaz selon la revendication 11, (a) dans les réseaux verticaux, l'oxyde et le composé contenant du silicium étant des réseaux verticaux approximativement normaux par rapport à la surface du substrat ; (b) dans les réseaux en treillis, l'oxyde et le composé contenant du silicium étant sous la forme d'un réseau ou d'une grille par rapport à la surface du substrat ; et (c) dans les réseaux parallèles, l'oxyde et le composé contenant du silicium étant parallèles l'un à l'autre par rapport à la surface du substrat.
  13. Procédé de réduction de la volatilisation du silicium à l'écart d'un article de moteur à turbine à gaz qui contient du silicium, ledit procédé comprenant :
    a) la fourniture d'un article comprenant un composite à matrice céramique ;
    b) la fourniture d'une surface extérieure dudit article qui est en contact avec des gaz à des températures élevées pendant le fonctionnement de l'article de moteur à turbine à gaz ; et
    c) la liaison d'une couche d'oxyde poreuse à au moins une partie de ladite surface extérieure de l'article, de telle sorte que le taux de volatilisation du silicium, à des températures élevées, à l'écart de ladite surface extérieure de l'article est réduit ;
    le composite à matrice céramique comprenant un composite à matrice céramique SiC-SiC ;
    la couche d'oxyde poreuse comprenant un mélange diphasique d'un oxyde et d'un composé contenant du silicium ;
    l'oxyde comprenant un ou plusieurs disilicates de terres rares (RE2Si2O7), aluminosilicates alcalino-terreux et/ou monosilicates de terres rares (RE2SiO5) ;
    une couche intermédiaire étant utilisée entre le substrat et la couche d'oxyde afin d'améliorer l'intégrité structurelle du substrat au moyen de la couche poreuse ;
    la couche intermédiaire comprenant un oxyde et du silicium ou un composé contenant du silicium, ou un mélange diphasique de silicium ou de carbure de silicium et un disilicate de terres rares, ou un mélange diphasique de nitrure de silicium et un monosilicate de terres rares.
  14. Procédé selon la revendication 11, la structure de l'oxyde et d'un composé contenant du silicium étant sous la forme de réseaux verticaux ou d'un réseau en treillis de l'oxyde et du silicium ou du composé contenant du silicium.
  15. Procédé selon la revendication 11, la couche d'oxyde étant chimiquement stable dans des environnements contenant de l'humidité et/ou ne présentant pas plus de 30 % de changement de volume négatif associé à une réaction avec de la vapeur d'eau.
  16. Procédé selon la revendication 11, une température élevée comprenant des températures de 1204,4 °C (2200 F) à 1537,77 °C (2800 F).
EP14712929.0A 2013-03-15 2014-03-05 Composite à matrice céramique et revêtements de barrière environnementale résistant à l'usure Active EP2971562B1 (fr)

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CA2905252C (fr) 2021-03-16
US20160024962A1 (en) 2016-01-28
EP2971562A1 (fr) 2016-01-20
CN105189932A (zh) 2015-12-23
US10094236B2 (en) 2018-10-09
CN105189932B (zh) 2018-04-24
WO2014149759A1 (fr) 2014-09-25
JP2016516153A (ja) 2016-06-02
BR112015023112A2 (pt) 2017-07-18
JP6568048B2 (ja) 2019-08-28
CA2905252A1 (fr) 2014-09-25

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